The present invention relates to novel reactive dyes, to a process for their preparation and to their use in the dyeing or printing of textile fibre materials.
The practice of dyeing using reactive dyes has recently led to higher demands being made on the quality of the dyeings and the profitability of the dyeing process. As a result, there continues to be a need for novel reactive dyes having improved properties, especially in respect of their application.
Dyeing nowadays requires reactive dyes that have sufficient substantivity and at the same time have good ease of washing off of unfixed dye. They should also have a good colour yield and high reactivity, the objective being to provide especially dyeings having high degrees of fixing. The known dyes do not satisfy these requirements in all properties.
The problem underlying the present invention is accordingly to find, for the dyeing and printing of fibre materials, novel improved reactive dyes having the qualities characterised above to a high degree. The novel dyes should especially be distinguished by high fixing yields and high fibre-dye bond stabilities. The dyes should also yield dyeings having good allround properties, for example fastness to light and to wetting.
It has been found that the problem posed is largely solved by the novel dyes defined herein-below, especially when the dyes are used for dyeing synthetic polyamide fibre materials.
The present invention therefore relates to reactive dyes of formula 
wherein
R1 is halogen, C1-C4alkyl, C1-C4alkoxy, C2-C4alkanoylamino, xcex1,xcex2-dihalopropionylamino or xcex1-haloacryloylamino,
X is halogen,
n is the number 0, 1 or 2, and
V is a radical of formula 
wherein
(R2)l denotes l identical or different substituents selected from the group halogen, hydroxy, nitro, sulfo, C1-C4alkyl and C1-C4alkoxy,
Y is xcex1,xcex2-dihalopropionylamino, xcex1-haloacryloylamino or a radical xe2x80x94CONHxe2x80x94(CH2)2-3xe2x80x94SO2xe2x80x94Z and
Z is vinyl or a radical xe2x80x94CH2CH2xe2x80x94U and U is a group removable under alkaline conditions,
m is the number 0 or 1, and
l is the number 0, 1, 2 or 3, with the proviso that
R1 is not xcex1,xcex2-dihalopropionylamino or xcex1-haloacryloylamino when V is a radical of formula (2) wherein Y is xcex1,xcex2-dihalopropionylamino or xcex1-haloacryloylamino.
The dyes of formula (1) according to the invention are fibre-reactive. Fibre-reactive compounds are to be understood as being those which are capable of reacting with the hydroxyl groups of cellulose, with the amino, carboxy, hydroxy or thiol groups in wool and silk or with the amino groups and, possibly, with the carboxy groups of synthetic polyamides, to form covalent chemical bonds.
The sulfo groups present in the dyes of formula (1) are each either in the form of their free acid or preferably in the form of a salt thereof. Salts that come into consideration include, for example, the alkali metal, alkaline earth metal or ammonium salts, salts of an organic amine or mixtures thereof. Examples that may be mentioned are sodium, lithium, potassium and ammonium salts, the salt of mono-, di- or tri-ethanolamine or Na/Li or Na/Li/NH4 mixed salts.
As C1-C4alkyl there come into consideration for R1 and R2 independently of one another e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl and isobutyl, preferably methyl or ethyl, especially methyl.
As C1-C4alkoxy there come into consideration for R1 and R2 independently of one another e.g. methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy and isobutoxy, preferably methoxy or ethoxy, especially methoxy.
As halogen there come into consideration for R1 and R2 independently of one another e.g. fluorine, chlorine and bromine, preferably chlorine or bromine, especially chlorine.
As C2-C4alkanoylamino there come into consideration for R. e.g. acetylamino and propionylamino, especially acetylamino.
As a group U removable under alkaline conditions there come into consideration, for example, xe2x80x94Cl, xe2x80x94Br, xe2x80x94F, xe2x80x94OSO3H, xe2x80x94SSO3H, xe2x80x94OCOxe2x80x94CH3, xe2x80x94OPO3H2, xe2x80x94OCOxe2x80x94C6H5, xe2x80x94OSO2xe2x80x94C1xe2x80x94C4alkyl and xe2x80x94OSO2xe2x80x94N(C1-C4alkyl)2. U is preferably a group of formula xe2x80x94Cl, xe2x80x94OSO3H, xe2x80x94SSO3H, xe2x80x94OCOxe2x80x94CH3, xe2x80x94OCOxe2x80x94C6H5 or xe2x80x94OPO3H2, especially xe2x80x94Cl or xe2x80x94OSO3H, more especially xe2x80x94Cl.
Examples of suitable radicals Z are accordingly vinyl, xcex2-bromo- or xcex2-chloro-ethyl, xcex2-acetoxy-ethyl, xcex2-benzoyloxyethyl, xcex2-phosphatoethyl, xcex2-sulfatoethyl and xcex2-thiosulfatoethyl. Z is preferably vinyl, xcex2-chloroethyl or xcex2-sulfatoethyl, especially vinyl or xcex2-chloroethyl.
The sulfo group on the naphthalene ring of the dye of formula (1) is either in the 3-position or the 4-position, preferably in the 3-position.
X is e.g. fluorine, chlorine or bromine, preferably fluorine or chlorine, especially chlorine.
In the reactive dyes of formula (1) according to the invention, R1 is preferably xcex1,xcex2-dihalo-propionylamino or xcex1-haloacryloylamino when V is a radical of formula (3).
n is preferably the number 0 or 1, especially the number 1.
m is preferably the number 0.
The radical of formula (2) in the dye of formula (1) is especially a radical of formula 
The radical of formula (3) in the dye of formula (1) is preferably a radical of formula 
especially of formula (3a).
(R2)l preferably denotes l identical or different substituents selected from the group halogen, hydroxy, nitro and sulfo.
l is preferably the number 0, 1 or 2, especially the number 0.
Y as xcex1,xcex2-dihalopropionylamino or xcex1-haloacryloylamino is preferably xcex1,xcex2-dibromopropionylamino, xcex1,xcex2-dichloropropionylamino, xcex1-bromoacryloylamino or xcex1-chloroacryloylamino, especially xcex1,xcex2-dibromopropionylamino or xcex1-bromoacryloylamino.
Y as a radical of formula xe2x80x94CONHxe2x80x94(CH2)2-3xe2x80x94SO2xe2x80x94Z is preferably a radical of formula xe2x80x94CONHxe2x80x94(CH2)2xe2x80x94SO2xe2x80x94Z, wherein Z has the definitions and preferred meanings given above, and especially a radical of formula xe2x80x94CONHxe2x80x94(CH2)2xe2x80x94SO2xe2x80x94(CH2)2xe2x80x94Cl or of formula xe2x80x94CONHxe2x80x94(CH2)2xe2x80x94SO2xe2x80x94CHxe2x95x90CH2.
Y is especially xcex1,xcex2-dibromopropionylamino, xcex1,xcex2-dichloropropionylamino, xcex1-bromoacryloylamino or xcex1-chloroacryloylamino, more especially xcex1,xcex2-dibromopropionylamino or xcex1-bromoacryloylamino.
R1 as xcex1,xcex2-dihalopropionylamino or xcex1-haloacryloylamino is preferably xcex1,xcex2-dibromopropionylamino, xcex1, xcex2-dichloropropionylamino, xcex1-bromoacryloylamino or xcex1-chloroacryloylamino, especially xcex1,xcex2-dibromopropionylamino or xcex1-bromoacryloylamino.
R1 is preferably methyl, ethyl, methoxy, ethoxy, xcex1,xcex2-dibromopropionylamino or xcex1-bromoacryloylamino.
R1 is especially methoxy, ethoxy, xcex1,xcex2-dibromopropionylamino or xcex1-bromoacryloylamino.
Preference is given to the reactive dyes of formula 
especially the reactive dye of formula (1a) wherein the sulfo group is bonded in the 3-position of the naphthalene ring.
Preference is also given to the reactive dyes of formula 
especially the reactive dye of formula (1b) wherein the sulfo group is bonded in the 3-position of the naphthalene ring.
The present invention relates also to a process for the preparation of reactive dyes of formula (1) which comprises reacting a compound of formula 
and an amine of formula
H2Nxe2x80x94Vxe2x80x83xe2x80x83(5) 
with a cyanuric halide in any desired order, R1, V and n having the definitions and preferred meanings given above.
Since the individual process steps can be carried out in different orders, including, if desired, simultaneously, various process variants are possible. The reaction is usually carried out stepwise, the order in which the single reactions between the individual reaction components is carried out advantageously being governed by the particular conditions. For example, about one molar equivalent of an amine of formula (5) is reacted with about one molar equivalent of a cyanuric halide and the resulting product is then condensed with about one molar equivalent of a compound of formula (4). In another process variant, for example about one molar equivalent of a compound of formula (4) is reacted with about one molar equivalent of a cyanuric halide and the resulting mixture is then condensed with about one molar equivalent of an amine of formula (5).
Suitable cyanuric halides are, for example, cyanuric chloride and cyanuric fluoride, especially cyanuric chloride.
The individual condensation reactions are carried out e.g. in accordance with processes known per se, generally in aqueous solution, at a temperature of e.g. from 0 to 50xc2x0 C., especially from 0 to 10xc2x0 C., and a pH of e.g. from 1 to 10, especially from 1 to 7.
Instead of the compound of formula (4) it is also possible to use the dye precursor of the compound of formula (4) and to convert the resulting intermediates into the desired dyes by diazotisation and coupling.
The end product can optionally also be subjected to a transformation reaction. Such a transformation reaction is, for example, the conversion of a reactive group R, or Y capable of vinylation into its vinyl form by treatment with dilute sodium hydroxide solution, for example the conversion of the xcex2-sulfatoethylsulfonyl or xcex2-chloroethylsulfonyl group into the vinyl-sulfonyl radical or the conversion of the xcex1,xcex2-dihalopropionylamino group into the xcex1-halo-acryloylamino radical. Such reactions are known per se. Such a transformation reaction is generally carried out in a neutral to alkaline medium at a temperature of e.g. from 20 to 70xc2x0 C., at a pH of e.g. from 6to 14.
Preference is given to a preparation process wherein an amine of formula 
wherein R1 and n are as defined above, is diazotised and coupled to a compound of formula 
wherein X and V are as defined above, and optionally the xcex1,xcex2-dihalopropionylamino radical present in the resulting reactive dye is converted into the xcex1-haloacryloylamino radical.
The diazotisation and coupling are effected in a manner known per se. For example, the diazotisation of the amine of formula (6) is generally carried out by the action of nitrous acid in aqueous mineral-acid-containing solution at low temperature, e.g. from 0 to 20xc2x0 C., while the coupling to the coupling component of formula (7) is carried out at acid to neutral pH values, especially at a pH of from 2 to 6.
In the process according to the invention for the preparation of the reactive dyes of formula (1), the substituents of the compounds of formulae (6) and (7) have the definitions and preferred meanings given above.
The compounds of formulae (4), (5), (6) and (7) are known or can be prepared analogously to known processes.
For example, compounds of formula (7) can be obtained by condensing a compound of formula 
with a cyanuric halide and condensing the resulting condensation product with an amine of formula (5) given above.
The condensation is effected in a manner known per se, e.g. in aqueous solution at a temperature of, for example, from 0 to 40xc2x0 C. and a pH of e.g. from 1 to 6. The condensation of the compound of formula (8) with a cyanuric halide, preferably cyanuric chloride, is preferably carried out at a temperature of from 0 to 10xc2x0 C. and a pH of from 1 to 3. The condensation of the resulting condensation product with the amine of formula (5) is carried out preferably at a temperature of from 0 to 30xc2x0 C. and a pH of from 4 to 6.
The reactive dyes of formula (1) according to the invention are suitable for dyeing or printing nitrogen-containing or hydroxyl-group-containing fibre materials, paper or leather, e.g. textile fibre materials of cellulose, silk and especially wool and synthetic polyamides.
Preference is given to the dyeing or printing of natural or synthetic polyamide fibre materials, especially synthetic polyamide fibre materials, e.g. polyamide-6 or polyamide-6.6.
The said textile material may be in an extremely wide variety of processing forms, e.g. in the form of fibres, yarns, woven fabrics or knitted fabrics.
The reactive dyes of formula (1) can be used for dyeing or printing in accordance with customary dyeing or printing processes. In addition to water and the dyes, the dyeing liquors or print pastes may comprise further additives, for example wetting agents, anti-foams, levelling agents or agents that influence the properties of the textile material, for example softeners, additives for flame-resistant finishes or dirt-, water- and oil-repellents and also water-softeners and natural or synthetic thickeners, e.g. alginates and cellulose ethers.
The reactive dyes of formula (1) yield level dyeings having good allround properties, especially good fastness to rubbing, to wetting, to wet rubbing and to light. They are also distinguished by uniform colour build-up, good affinity, high reactivity, good fixing ability and very good build-up ability. The dyes according to the invention have good water-solubility and are readily combinable with other dyes.
The following Examples serve to illustrate the invention. The temperatures are given in degrees Celsius. Unless otherwise indicated, parts are parts by weight and percentages relate to percent by weight. Parts by weight relate to parts by volume in a ratio of kilograms to liters.